EP2565221B1 - Verfahren zur herstellung eines kondensatorfilms - Google Patents

Verfahren zur herstellung eines kondensatorfilms Download PDF

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Publication number
EP2565221B1
EP2565221B1 EP11179322.0A EP11179322A EP2565221B1 EP 2565221 B1 EP2565221 B1 EP 2565221B1 EP 11179322 A EP11179322 A EP 11179322A EP 2565221 B1 EP2565221 B1 EP 2565221B1
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EP
European Patent Office
Prior art keywords
polypropylene
scs
catalyst system
solid catalyst
compound
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Active
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EP11179322.0A
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English (en)
French (fr)
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EP2565221A1 (de
EP2565221B2 (de
Inventor
Peter Denifl
Pirjo Jääskeläinen
Timo Leinonen
Bo Malm
Anders E. Nymark
Torvald Vestberg
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Borealis AG
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Borealis AG
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Application filed by Borealis AG filed Critical Borealis AG
Priority to EP11179322.0A priority Critical patent/EP2565221B2/de
Priority to KR1020147007757A priority patent/KR101663393B1/ko
Priority to PCT/EP2012/066729 priority patent/WO2013030210A1/en
Priority to US14/240,696 priority patent/US10253115B2/en
Priority to CN201280041262.1A priority patent/CN103764732B/zh
Priority to SG2014011357A priority patent/SG2014011357A/en
Priority to JP2014527636A priority patent/JP5789721B2/ja
Publication of EP2565221A1 publication Critical patent/EP2565221A1/de
Publication of EP2565221B1 publication Critical patent/EP2565221B1/de
Publication of EP2565221B2 publication Critical patent/EP2565221B2/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • H01G4/186—Organic dielectrics of synthetic material, e.g. derivatives of cellulose halogenated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/32—Wound capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0032—Processes of manufacture formation of the dielectric layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present invention is directed to a new process for the manufacture of a capacitor film.
  • Polypropylene is the material of choice in the field of film capacitors as its chain lacks any kind of polar groups which orient under electrical field stress. As a result, polypropylene intrinsically possesses a low loss factor and high volume resistivity. These properties, combined with a relatively high dielectric constant and self healing character in the capacitor as well good mechanical properties, like high melting temperature and high stiffness, make polypropylene so valuable in this technical field.
  • the dielectric strength or the breakdown voltage of polypropylene can be further increased in case it is biaxially oriented which is obtained by stretching a heated sheet of film in two opposing directions, longitudinal and transverse machine directions, inducing a more perfect crystalline formation and orientation.
  • the dielectric film made from such a polypropylene contains considerable amounts of polar residues, like chlorine, aluminium, titanium, magnesium or silicon originating from the used Ziegler-Natta catalyst. These residues decrease the resistivity, i.e. increase the conductivity of the polymers, making the polymer unsuitable to be used as such in applications, where very low conductivity is needed, like in films for capacitors. Accordingly to make polypropylene commercially attractive in this technical field it must be troublesome purified, typically washed in order to remove the undesired residues from the polymer material, a process which is time consuming and cost-intensive.
  • washing liquid typically used comprises organic hydrocarbon solvents having polar groups, like hydroxyl groups, e.g. propanol.
  • Polypropylenes with low levels of impurities including metallic and non-metallic impurities, like aluminium, titanium, silicon, and halogen (such as Cl and F) are produced in the presence of supported single-site catalysts, as for instance described in WO 02/16455 A1 .
  • polymers disclosed in this application are to be washed in order to remove undesired impurities and residues.
  • EP 1 741 752 relates to a polypropylene with a low amount of impurities, in particular a low amount of aluminum and boron residues.
  • US 5,573,840 describes a polymeric insulating material which is said to have a high dielectric breakdown voltage.
  • the material comprises polypropylene which has been obtained in a yield of at least 300,000 g/g-Ti based on titanium in a catalyst upon polymerization, contains ash in an amount not greater than 40 ppm by weight when analyzed by completely burning the polypropylene in air, said ash containing titanium in an amount not greater than 1 ppm by weight based on the weight of the polypropylene, and also contains chlorine in an amount not greater than 2 ppm by weight and boiling n-heptane soluble matter in an amount not smaller than 1 wt.-% but not greater than 10 wt.-%.
  • JP 11-240915 relates to a method of purification of polypropylene comprising adding 0.1 to 1.5 wt.-% of ethylene to polypropylene powder and performing polymerisation with a catalyst comprising magnesium, titanium and halogen having an efficiency of 40 kg/PP/g. Subsequently, an aqueous phase containing a low molecular weight component is contacted with the propylene slurry containing 30 wt.-% or more of alcohol.
  • WO 02/092640 relates to low bulk density polypropylene homopolymers and copolymers obtained using a second-generation Ziegler-Natta catalyst system.
  • the object of the present invention is to provide a process which enables a skilled person to produce a capacitor film with desired electrical properties without the need to use a purified polypropylene, like a polypropylene which is washed in order to remove undesired residues as explained above.
  • the finding of the present invention is to use a polypropylene containing particles of small particle sizes, preferably of nano sizes. Especially it has been found that desired electrical properties are possible to achieve, if said small particles are distributed already during polymerization step instead of adding separately e.g. some nanoparticles to the ready polymers. Distribution of the small particles, preferably of nano sizes, already during polymerization, enables even distribution of the particles and thus desired electrical properties are achieved. Thus, according to the present invention it has been surprisingly found that by using during the polypropylene polymerization a catalyst system which breaks at a very early stage of polymerization in very small, nano-size particles the desired electrical properties are achieved.
  • Said solid catalyst system (SCS) used in the process of the invention can further comprise (iv) solid catalytically inactive material the amount of which is less than 40.0 wt-%.
  • solid catalyst system used in the process of the invention
  • the solid catalyst system (SCS) comprises said solid catalytically inactive material
  • the solid catalyst system (SCS) comprises inclusions comprising or being composed of said catalytically inactive solid material in amounts of up to 30 wt.-%, more preferably up to 20 wt-%, still more preferably not more than 10 wt-%, based on the solid catalyst system (SCS).
  • the solid catalyst system (SCS) used in the invention is obtained by a process comprising contacting
  • said solid catalyst system comprises
  • Said solid catalyst system (SCS) used in the process of the invention can further comprise (iv) solid catalytically inactive material the amount of which is less than 40,0 wt-%.
  • solid catalyst system used in the process of the invention
  • the catalyst comprising the solid catalyst system (SCS) is distributed in the polypropylene (PP) as nanosized catalyst fragments (F).
  • the distribution of the nanosized catalyst fragments (F) occurs due to fragmentation of the catalyst and of the solid catalyst system (SCS), respectively, at a very early stage of the polymerization process in step (a). This early fragmentation enables even distribution of fragments in the polymer.
  • the polypropylene (PP) of the first and second embodiment is preferably a random propylene copolymer (R-PP) or a propylene homopolymer (H-PP), the latter especially preferred.
  • capacitor film and/or the polypropylene (PP) of the first and second embodiment has/have
  • the process can be defined as a process for producing of a capacitor film comprising the step of subjecting a polypropylene (PP) with ⁇ 2,1> erythro regiodefects of equal or below 0.4 mol.-% determined by 13 C-NMR spectroscopy to a film forming process, wherein said polypropylene (PP) has additionally an breakdown voltage at least 350 VDC/ ⁇ m measured on a biaxially oriented polypropylene (BOPP) film made from said polypropylene (PP) at a draw ratio in machine direction and in transverse direction of 4.5 x 9.5.
  • PP polypropylene
  • BOPP biaxially oriented polypropylene
  • the above polypropylene (PP) is preferably a random propylene copolymer (R-PP) or a propylene homopolymer (H-PP), the latter especially preferred.
  • the polypropylene (PP) comprises nano-sized catalyst fragments (F) being distributed in said polypropylene (PP).
  • the nanosized catalyst fragments (F) originate from a catalyst and a solid catalyst system (SCS), respectively.
  • propylene and optionally ethylene and/or at least one C 4 to C 10 ⁇ -olefin is polymerized in the presence of a catalyst comprising
  • Said solid catalyst system (SCS) used in the process of the invention can further comprise (iv) solid catalytically inactive material the amount of which is less than 40.0 wt-%.
  • solid catalyst system used in the process of the invention
  • the solid catalyst system (SCS) comprises said solid catalytically inactive material
  • the solid catalyst system (SCS) comprises inclusions comprising or being composed of said solid material in amounts of up to 30 wt.-% more preferably up to 20 wt-%, still more preferably not more than 10 wt-%, based on the solid catalyst system (SCS).
  • the solid catalyst system (SCS) of the third embodiment is obtained by a process comprising contacting
  • the capacitor films according to the invention have good electrical properties even though the films might contain even considerable amounts of residues indication of which is the higher ash content as normally allowed in products having good electrical properties. Without bound to any theories, it is believed that the ash contained in the polymer prepared as described here differs from the ones originating from conventionally supported Ziegler-Natta catalysts.
  • the present invention is related to the use of a specific type of catalyst system for producing propylene polymer suitable to be used as capacitator film (or having electrical properties suitable for use in capacitator film applications) and to be used as such, i.e. without any need to remove the catalyst residues out of the polymer, i.e. without any purification, like washing step.
  • Essential aspect of the present invention is that a specific polypropylene (PP) is used for the manufacture of the capacitor film.
  • PP polypropylene
  • the polypropylene (PP) is featured by a rather low comonomer content. Accordingly it is preferred that the capacitor film and/or the polypropylene (PP) has/have a comonomer content of equal or below 2.0 wt.-%, more preferably equal or below 1.5 wt.-%, yet more preferably equal or below 1.0 wt.-% or most preferable less than 0.5 wt-%
  • polypropylene is preferably a random propylene copolymer (R-PP) or a propylene homopolymer (H-PP), the latter is especially preferred.
  • the polypropylene is a random propylene copolymer (R-PP) it comprises monomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to C 20 ⁇ -olefins, in particular ethylene and/or C 4 to C 10 ⁇ -olefins, e.g. 1-butene and/or 1-hexene.
  • R-PP random propylene copolymer
  • the random propylene copolymer (R-PP) comprises, especially consists of, monomers copolymerizable with propylene selected from the group consisting of ethylene, 1-butene and 1-hexene.
  • the random propylene copolymer (R-PP) comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the random propylene copolymer (R-PP) comprises units derivable from ethylene and propylene only.
  • the comonomer content in the random propylene copolymer (R-PP) is preferably in the range of more than 0.5 to 2.0 wt.-%, still more preferably in the range of more than 0.5 to 1.0 wt.-%, yet more preferably in the range of more than 0.5 to 0.8 wt.-%.
  • the expression homopolymer used in the instant invention relates to a polypropylene (PP) that consists substantially, i.e. of equal or more than 99.5 wt.-%, more preferably of equal or more than 99.8 wt.-%, of propylene units. In a preferred embodiment only propylene units in the propylene homopolymer (H-PP) are detectable.
  • PP polypropylene
  • the polypropylene (PP) is isotactic. Accordingly it is appreciated that the polypropylene (PP) has a rather high pentad concentration (mmmm%) i.e. higher than 90 %, more preferably higher than 92 %, still more preferably higher than 93 % and even higher than 95 %, like at least 97 % are possible.
  • mmmm% pentad concentration
  • a further characteristic of the capacitor film and/or the polypropylene (PP) is the low amount of misinsertions of propylene within the polymer chain, which indicates that the polypropylene (PP) is produced in the presence of a catalyst as defined below, i.e. in the presence of a Ziegler-Natta catalyst.
  • the capacitor film and/or the polypropylene (PP) is/are preferably featured by low amount of ⁇ 2,1> regiodefects, i.e. of equal or below 0.4 mol.-%, more preferably of equal or below than 0.2 mol.-%, like of not more than 0.1 mol.-%, determined by 13 C-NMR spectroscopy.
  • no ⁇ 2,1> regiodefects are detectable, i.e. the amount of ⁇ 2,1> regiodefects is 0.0 mol.-%.
  • the capacitor film and/or the polypropylene can have a xylene cold soluble content (XCS) in a broad range, i.e. up to 6.0 wt.-%. Accordingly the capacitor film and/or the polypropylene (PP) may have a xylene cold soluble content (XCS) in the range of 0.3 to 6.0 wt.-%, more preferably 0.5 to 5.5 wt.-%, still more preferably 1.0 to 4.0 wt.-%.
  • XCS xylene cold soluble content
  • the amount of xylene cold soluble (XCS) additionally indicates that the capacitor film and/or the polypropylene (PP) is/are preferably free of any elastomeric polymer component, like an ethylene propylene rubber.
  • the capacitor film and/or the polypropylene (PP) shall be not a heterophasic polypropylene, i.e. a system consisting of a polypropylene matrix in which an elastomeric phase is dispersed. Such systems are featured by a rather high xylene cold soluble content.
  • a further aspect of the instant invention is that the capacitor film and/or polypropylene (PP) has/have a rather high melting point. Accordingly it is appreciated that the capacitor film and/or the polypropylene (PP) according to this invention has/have a melting temperature (T m ) determined by differential scanning calorimetry (DSC) of at least 155 °C, more preferably of at least 158 °C, yet more preferably of at least 160 °C.
  • T m melting temperature determined by differential scanning calorimetry (DSC) of at least 155 °C, more preferably of at least 158 °C, yet more preferably of at least 160 °C.
  • the melting temperature (T m ) determined by differential scanning calorimetry (DSC) of the capacitor film and/or of the polypropylene is in the range of 155 to 168 °C, more preferably in the range of 155 to 165 °C, still more preferably in the range of 157 to 163 °C, like in the range of 159 to 163°C
  • the capacitor film and/or the polypropylene (PP) has/have a rather high crystallization temperature (T c ).
  • T c crystallization temperature
  • the capacitor film and/or the polypropylene (PP) has/have crystallization temperature (T c ) determined by differential scanning calorimetry (DSC) of at least 110 °C, more preferably of at least 111 °C.
  • DSC differential scanning calorimetry
  • the capacitor film and/or the polypropylene (PP) has/have preferably a crystallization temperature (T c ) determined by differential scanning calorimetry (DSC) in the range of 110 to 120 °C, more preferably in the range of 110 to 115 °C.
  • the polypropylene (PP) has a weight average molecular weight (M w ) from 200,000 to 600,000 g/mol, more preferably from 250,000 to 450,000 g/mol.
  • a broad molecular weight distribution (MWD) improves the processability of the polypropylene. Accordingly it is appreciated that the molecular weight distribution (MWD) of the capacitor film and/or the polypropylene (PP) is at least 2.8, more preferably at least 3.0, like at least 3.3 In a preferred embodiment the molecular weight distribution (MWD) is preferably between 3.0 to 10.0, still more preferably in the range of 3.5 to 8.0.
  • the capacitor film and/or the polypropylene (PP) has/have a melt flow rate MFR 2 (230 °C) of more than 0.5 g/10min, more preferably of more than 1.0 g/10min. Accordingly it is appreciated that the melt flow rate MFR 2 (230 °C) is in the range of 0.5 to 8.0 g/10min, more preferably in the range of 1.0 to 6.0 g/10min, still more preferably in the range of 1.5 to 4.0 g/10min.
  • the polypropylene (PP) is of linear structure and thus does not show (or nearly does not show) a kind of branching. Accordingly it is appreciated that the capacitor film and/or the polypropylene (PP) has/have preferably a branching index g' of not less than 0.9, preferably more than 0.9, like at least 0.95. In other words if the capacitor film and/or the polypropylene (PP) has/have some kind of branching it shall be rather moderate. Accordingly the branching index g' of the capacitor film and/or the polypropylene (PP) is preferably in the range of 0.9 to 1.0, more preferably in the range of more than 0.9 to 1.0, like in the range of 0.96 to 1.0. In an especially preferred embodiment the capacitor film and/or the polypropylene (PP) shows/show no branching, i.e. the capacitor film and/or the polypropylene has/have a branching index g' of 1.0.
  • the polypropylene (PP) of the present invention is preferably featured by the presence of unique catalyst residues. More precisely the polypropylene (PP) is preferably characterized by catalyst fragments (F) being of nanosized range. These fragments (F) preferably originate from a catalyst comprising a solid catalyst system (SCS) used for the manufacture of the polypropylene (PP).
  • SCS solid catalyst system
  • the used process for the manufacture of the polypropylene (PP) including the specific catalyst comprising the solid catalyst system (SCS) is defined in more detail below.
  • nanosized indicates that the catalyst fragments (F) have a mean particle size d50 of below 1 ⁇ m, more preferably of below 800 nm, still more preferably 20 to 600 nm, yet more preferably 30 to 500 nm, like 30 to 300 nm.
  • even distribution (or similar terms like “evenly distributed") of the nanosized catalyst fragments (F) in the polypropylene (PP) shall indicate that the fragments (F) are not localized in one specific area of the polypropylene (PP) but anywhere in the polypropylene (PP).
  • This expression shall in particular indicates that the fragments (F) originate from a catalyst comprising the solid catalyst system (SCS) which breaks at very early stage of polymerization of the polypropylene (PP) in very small, nano-size particles and thus are evenly distributed in the growing polypropylene (PP).
  • SCS solid catalyst system
  • the even distribution of the nanosized (catalyst) fragements (F) in the polypropylene (PP) can only be accomplished by using the catalyst comprising the solid catalyst system (SCS) as disclosed herein, which breaks apart at the very early stage of the polymerization process of the polypropylene (PP).
  • SCS solid catalyst system
  • the polypropylene (PP) containing nanosized catalyst fragments (F), which originate from the catalyst comprising solid catalyst system (SCS), have interesting electrical properties, i.e. low electrical conductivity.
  • the nanosized catalyst fragments (F) described herein do not deteriorate the electrical properties of the polypropylene (PP), and thus, the amount of fragments is not a critical issue.
  • the specific nanosized catalyst fragments (F) are useful to lower electrical conductivity compared to conventional catalyst residues. As a result of this, a costly and troublesome purifying step can be omitted.
  • An indicator of the amount of residues, i.e. catalyst fragments (F), in capacitor film and/or in the polypropylene(PP) is the ash content.
  • the ash content of a polypropylene in the field of capacitors must be rather low in order to avoid deterioration in electrical properties.
  • the polymer used for capacitator film should have the ash content below 30 ppm, preferably below 20 ppm (ISO 3451-1).
  • the amount of ash is not any restrictive feature in the polypropylene (PP) used in the instant invention, i.e.
  • the capacitor film and/or the polypropylene (PP) of the invention can have an ash content of from very small, like below 30 ppm up to several hundreds of ppm, like up to 500 ppm.
  • the capacitor film and/or the polypropylene (PP) may contain 5 to 500 ppm ash content, preferably 10 to 400 ppm.
  • the ash content is more than 30 to 500 ppm, more preferably in the range of 40 to 400 ppm, like in the range of 50 to 300 ppm.
  • capacitor film and/or the polypropylene (PP) is/are featured by
  • the capacitor film and/or the polypropylene (PP) is/are featured by an electrical conductivity of 70 fS/m or less, more preferably of ⁇ 0.01 (lower values not detectable by the DC conductivity measurement) to 60 fS/m, more preferably of ⁇ 0.01 to 40 fS/m, more preferably of ⁇ 0.01 to 30 fS/m, still more preferably of ⁇ 0.01 to 20 fS/m, still yet more preferably ⁇ 0.01 to 10 fS/m when measured according to DC conductivity method ASTM D257 as described in the "Example Section".
  • the polypropylene (PP) as defined above is subjected to a film forming process obtaining thereby a capacitor film.
  • the polypropylene (PP) is the only polymer within the capacitor film.
  • the capacitor film may contain additives but preferably no other polymer.
  • the remaining part up to 100.0 wt-% may be accomplished by additives known in the art, like antioxidants.
  • this remaining part shall be not more than 5.0 wt.-%, preferably not more than 2.0 wt.-%, like not more than 1.0 wt.%, within the capacitor film.
  • the capacitor film preferably comprises more than 95 wt.-%, more preferably more 98 wt.-%, like more than 99.0 wt.-%, of the polypropylene (PP) as defined herein.
  • the thickness of the capacitor film can be up to 15.0 ⁇ m, however, typically the capacitor film has a thickness of not more than 12.0 ⁇ m, preferably not more than 10.0 ⁇ m, more preferably not more than 8.0 ⁇ m, yet more preferably in the range of 2.5 to 10 ⁇ m, like in the range of 3.0 to 8,0 ⁇ m.
  • the capacitor film is a biaxially oriented film, i.e. the polypropylene (PP) as defined above or any mixtures (blends) comprising the polypropylene (PP) has/have been subjected to a drawing process obtaining thereby a biaxially oriented polymer.
  • capacitor film preferably contains the polypropylene (PP) as only polymer and thus it is preferably a biaxially oriented polypropylene (BOPP) made from said polypropylene (PP).
  • the capacitor film i.e. the biaxially oriented polypropylene (BOPP)
  • BOPP biaxially oriented polypropylene
  • the capacitor film has a draw ratio in machine direction of at least 3.0 and a draw ratio in transverse direction of at least 3.0.
  • Such ratios are appreciated as commercial biaxially oriented polypropylene films must be stretchable at least to the above defined extent without breaking.
  • the length of the sample increases during stretching in longitudinal direction and the draw ratio in longitudinal direction calculates from the ratio of current length over original sample length. Subsequently, the sample is stretched in transverse direction where the width of the sample is increasing. Hence, the draw ratio calculates from the current width of the sample over the original width of the sample.
  • the draw ratio in machine direction of the capacitor film i.e.
  • the biaxially oriented polypropylene ranges from 3.5 to 8.0, more preferably from 4.5 to 6.5.
  • the draw ratio in transverse direction of the capacitor film, i.e. the biaxially polypropylene (BOPP) ranges preferably from 4.0 to 15.0, more preferably from 6.0 to 10,0.
  • Temperature range during stretching is in general 100 °C to 180 °C.
  • the capacitor film i.e. the biaxially oriented polypropylene (BOPP), preferably is produced from the polypropylene (PP) as defined above, the properties given for the polypropylene (PP) are equally applicable for the capacitor film if not specified differently.
  • PP polypropylene
  • the present invention is not only directed to a process for the manufacture of a capacitor film but also to the capacitor film comprising the polypropylene (PP).
  • PP polypropylene
  • all information provided in the section polypropylene (PP) and capacitor film are also regarded as product related features. Accordingly the present invention is in particular directed to a capacitor film as defined in the claims 18 and 19.
  • Catalyst comprising a solid catalyst system (SCS)
  • the specific polypropylene (PP) as defined above and used for the manufacture of the capacitor film is obtainable, preferably obtained, by the use of a catalyst comprising a specific solid catalyst system (SCS). Accordingly in the following the catalyst comprising the solid catalyst system (SCS), its preparation, as well as the polymerization process of the instant polypropylene (PP) will be described in more detail.
  • SCS solid catalyst system
  • the catalyst of the instant comprises
  • the solid catalyst system (SCS) used preferably comprises
  • said solid catalyst system has
  • a remarkable feature of the used catalyst system (SCS) is that it is of solid form.
  • the aggregate state (solid state) of the catalyst system (SCS) differs from the aggregate state of the reactants, i.e. the propylene and optionally other ⁇ -olefins used.
  • the solid catalyst system (SCS) used in the present invention is a so-called self-supported catalyst system, or in other words the solid catalyst system (SCS) used does not comprise external support material.
  • the purpose of such "external support material” is that the active catalyst species are deposited on the solid support material and in the optional pores of said solid support material, respectively.
  • Typical external support materials are organic or inorganic support materials, like silica, MgCl 2 or porous polymeric material. These inert external support materials are generally used in amounts of at least 50 wt.-%, more preferably of at least 70 wt.-%.
  • the catalyst used in the present invention does not contain external support material as defined above.
  • the solid catalyst system (SCS) may comprises catalytically inactive solid material in amounts of less than 40 wt.-% based on the solid catalyst system (SCS). This material does not act as support material, i.e. it is not used in order to get a solid catalyst system.
  • This catalytically inactive solid material is present during the solid catalyst system (SCS) preparation and thus is not added externally (subsequent to the catalyst preparation) as it is the case for conventional supported catalyst systems.
  • the amount of such catalytically inactive solid material within the obtained solid catalyst system (SCS) is preferably less than 30.0 wt.%, yet more preferably below 20.0 wt.-%, or preferably below 10 wt-%, based on the solid catalyst system (SCS).
  • This catalytically inactive solid material is nano-sized as will be disclosed in more detail below.
  • the solid catalyst system has a surface area measured according to the commonly known BET method with N 2 gas as analysis adsorptive (ASTM D 3663) of less than 30 m 2 /g, e.g. less than 20 m 2 /g. In some embodiments the surface area is more preferably of less than 15 m 2 /g, yet more preferably of less than 10 m 2 /g. In some embodiments, the solid catalyst system (SCS) shows a surface area of 5 m 2 /g or less, which is the lowest detection limit with the methods used in the present invention.
  • the solid catalyst system (SCS) can be additionally defined by the pore volume measured according to ASTM 4641.
  • the solid catalyst system (SCS) has a pore volume of less than 1.0 ml/g, although higher pore volumes are possible in some embodiments.
  • the pore volume is more preferably of less than 0.5 ml/g, still more preferably of less than 0.3 ml/g and even less than 0.2 ml/g.
  • the pore volume is not detectable when determined according to ASTM 4641.
  • the solid catalyst system typically has a mean particle size (d50) of not more than 500 ⁇ m, i.e. preferably in the range of 2 to 500 ⁇ m, more preferably 5 to 200 ⁇ m. It is in particular preferred that the mean particle size (d50) is below 100 ⁇ m, still more preferably below 80 ⁇ m. A preferred range for the mean particle size (d50) is 5 to 80 ⁇ m, and in some embodiments 10 to 60 ⁇ m.
  • the SPAN value indicating the broadness of particle size distribution
  • solid catalyst systems (SCS) produced by the emulsion-solidification method have SPAN values below 2.0, i.e. in the range of 0.5 to below 2.0, like 0.7 to 1.5
  • the SPAN values of the solid catalyst systems (SCS) obtained by more traditional precipitation method are of at least 2.0, more preferably of at least 3.0, yet more preferably of at least 4.0, like in the range of 4.0 to 7.0.
  • the solid catalyst system (SCS) has SPAN values below 2.0, i.e. in the range of 0.5 to below 2.0, like 0.7 to 1.5.
  • solid catalyst system may comprise inclusions.
  • Inclusions in accordance with the present invention do not comprise catalytically active sites and may be present in the form of hollow voids, in the form of liquid-filled hollow voids, in the form of hollow voids partially filled with liquid, in the form of solid material or in the form of hollow voids partially filled with solid material.
  • the inclusions are solid material, i.e. catalytically inactive solid material.
  • the solid catalyst system preferably comprises solid material, wherein said material does not comprise catalytically active sites and optionally has a specific surface area below 500 m 2 /g, and/or a mean particle size (d50) below 200 nm.
  • the expression "does not comprise catalytically active sites” or “catalytically inactive” shall in particular indicate that the solid material does not comprise, i.e. does not consist of, components and compounds, like transition metal compounds of group 3 to 10 of the periodic table (IUPAC), which has catalytic activity in polymerization processes.
  • the solid material is catalytically inert in polymerization processes, in particular in polymerization processes for the preparation of polyolefin, like polypropylene or polyethylene.
  • Such a catalytically inactive solid material is dispersed within the solid catalyst system (SCS).
  • the solid catalyst system (SCS) can be seen also as a matrix in which the catalytically inactive solid material is dispersed, i.e. form a dispersed phase within the matrix phase of the solid catalyst system (SCS).
  • the matrix is then constituted by the catalytically active components as defined herein, in particular by the transition metal compounds of groups 3 to 10 of the periodic table (IUPAC) and optionally the metal compounds of groups 1 to 3 of the periodic table (IUPAC).
  • IUPAC transition metal compounds of groups 3 to 10 of the periodic table
  • IUPAC transition metal compounds of groups 1 to 3 of the periodic table
  • all the other catalytic compounds as defined in the instant invention can additionally constitute to the matrix of the solid catalyst system (SCS) in which the catalytically inactive solid material is dispersed.
  • the catalytically inactive solid material usually constitutes only a minor part of the total mass of the solid catalyst system (SCS). Accordingly the solid catalyst system (SCS) comprises less than 40 wt.-% , preferably less than 30 wt-% catalytically inactive solid material, more preferably less than 20 wt.-%. It is in particular preferred that the solid catalyst system (SCS) comprises the catalytically inactive solid material, if present in the solid catalyst system (SCS), in the range of 1 to 30 wt.-%, more preferably in the range of 1 to 20 wt.-% and yet more preferably in the range of 1 to 10 wt.-%.
  • the catalytically inactive solid material may be of any desired shape, including spherical as well as elongated shapes and irregular shapes.
  • the catalytically inactive solid material in accordance with the present invention may have a plate-like shape or they may be long and narrow, for example in the shape of a fiber.
  • Preferred catalytically inactive solid material are inorganic materials as well as organic, in particular organic polymeric materials, suitable examples being nano-materials, such as silica, montmorillonite, carbon black, graphite, zeolites, alumina, as well as other inorganic particles, including glass nano-beads or any combination thereof.
  • Suitable organic particles, in particular polymeric organic particles are nano-beads made from polymers such as polystyrene, or other polymeric materials.
  • the catalytically inactive solid material employed of the solid catalyst system (SCS) has to be inert towards the catalytically active sites, during the preparation of the solid catalyst system (SCS) as well as during the subsequent use in polymerization reactions. This means that the catalytically inactive solid material is not to be interfered in the formation of active centres.
  • the catalytically inactive solid material is selected form spherical particles of nano-scale consisting of SiO 2 , polymeric materials and/or Al 2 O 3 .
  • the catalytically inactive solid material has a mean particle size (d50) of equal or below 200 nm, more preferred equal or below 150 nm, still more preferred below 100 nm. Accordingly it is preferred that the catalytically inactive solid material has a mean particle size (d50) of 10 to 200 nm, more preferred 10 to 100 nm, still more preferably from 10 to 90 nm, yet more preferred 10 to 80 nm.
  • the solid catalyst system (SCS) is preferably obtainable, i.e. obtained, by a process comprising contacting
  • solid catalyst system preparation of the solid catalyst system (SCS) is that neither the complex (C) nor the transition metal compound (CT) are present in solid form during the catalyst system (SCS) preparation, as it is the case for supported catalyst systems.
  • the catalytically inactive solid material if present, can be added to the system during the preparation either to (a) or (b) prior to contacting or after contacting, but before transforming the liquid catalyst into solid form.
  • the metal compound (CM) used for the preparation of the complex (C) may be any metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC). However it is preferred that the complex (C) is a Group 2 metal complex, even more preferred a magnesium complex. Accordingly it is appreciated that the metal compound (CM) used in the preparation of said complex (C) is a Group 2 metal compound, like a magnesium compound.
  • the metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), preferably from the Group 2 metal compound, like from the magnesium compound, is usually titaniumless.
  • the magnesium compound is provided by reacting an alkyl magnesium compound and/or a magnesium dihalide with an alcohol.
  • at least one magnesium compound precursor selected from the group consisting of a dialkyl magnesium R 2 Mg, an alkyl magnesium alkoxide RMgOR, wherein each R is an identical or a different C 1 to C 20 alkyl, and a magnesium dihalide MgX 2 , wherein X is a halogen
  • at least one alcohol selected from the group consisting of monohydric alcohols R'OH and polyhydric alcohols R'(OH) m , wherein R' is a C 1 to 20 hydrocarbyl group and m is an integer selected from 2, 3 ,4 ,5 and 6, to give said magnesium compound (CM).
  • R' is the same or different in the formulas R'OH and R'(OH) m .
  • alcohol can contain an additional oxygen bearing moiety being different to a hydroxyl group, e.g. an ether group.
  • the R of the dialkyl magnesium is preferably an identical or different C 4 to C 12 alkyl.
  • Typical magnesium alkyls are ethylbutyl magnesium, dibutyl magnesium, dipropyl magnesium, propylbutyl magnesium, dipentyl magnesium, butylpentyl magnesium, butyloctyl magnesium and dioctyl magnesium.
  • Typical alkyl-alkoxy magnesium compounds are ethyl magnesium butoxide, magnesium dibutoxide, butyl magnesium pentoxide, magnesium dipentoxide, octyl magnesium butoxide and octyl magnesium octoxide.
  • one R is a butyl group and the other R of R 2 Mg is an octyl group, i.e. the dialkyl magnesium compound is butyl octyl magnesium.
  • Typical polyhydric alcohols are ethylene glycol, propene glycol, trimethylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, pinacol, diethylene glycol, triethylene glycol, glycerol, trimethylol propane and pentaerythritol.
  • the polyhydric alcohol is selected from the group consisting of ethylene glycol, 2-butyl-2-ethyl-1, 3-propanediol and glycerol.
  • the reaction conditions used to obtain the metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), preferably the metal compound (CM) of Group 2, even more preferred the magnesium compound, may vary according to the used reactants and agents.
  • said magnesium compound precursor is reacted with said at least one alcohol at temperature of 30 to 80 °C for 10 to 90 min, preferably about 30 min.
  • CM metal compound which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), preferably the metal compound of Group 2, even more preferred the magnesium compound
  • said compound (CM) is further reacted with an electron donor (E) or electron donor precursor (EP) as known in the prior art.
  • the electron donor (E) is preferably a mono- or diester of a carboxylic acid or diacid, or an ether compound.
  • Said carboxylic acid ester or diester e.g. the mono- or diester of the aromatic or aliphatic, saturated or unsaturated carboxylic acid or diacid, can be formed in situ by reaction of an carboxylic acid halide or diacid halide, i.e.
  • a preferred electron donor precursor EP
  • a C 2 to C 16 alkanol and/or diol optionally containing an additional oxygen bearing moiety being different to a hydroxyl group, e.g. an ether group.
  • CM metal compound
  • said metal compound (CM) reacts with an electron donor precursor (EP), i.e. with a dicarboxylic acid dihalide having preferably the formula (I) wherein
  • non-aromatic dicarboxylic acid dihalides the group consisting of maleic acid dihalide, fumaric acid dihalide and their R" substituted derivatives such as citraconic acid dihalide and mesaconic acid dihalide, respectively, are the most important.
  • dicarboxylic acid dihalides the group consisting of phthalic acid dihalide (1,2-benzene dicarboxylic acid dihalide), its hydrogenate 1,2-cyclohexane dicarboxylic acid dihalide, and their derivatives, are the most important.
  • phthalic acid dihalide 1,2-benzene dicarboxylic acid dihalide
  • hydrogenate 1,2-cyclohexane dicarboxylic acid dihalide
  • derivatives are the most important.
  • dicarboxylic acid dihalide is phthaloyl dichloride.
  • the magnesium compound is reacted with the dicarboxylic acid halide in a molar ratio Mg total added /dicarboxylic acid halide of 1 : 1 and 1 : 0.1, preferably between 1 : 0. 6 and 1 : 0. 25.
  • the metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), more preferably the metal compound of Group 2, even more preferably the magnesium compound, is reacted with the electron donor (E) or with the electron donor precursor (EP), i.e. the dicarboxylic acid dihalide, under at least one of the following conditions:
  • the organic solvent used for the preparation of the complex (C) can be any organic solvent as long as it is ensured that the complex (C) is dissolved at ambient temperatures, i.e. at temperatures up to 80 °C (20 to 80 °C). Accordingly it is appreciated that the organic solvent comprises, preferably consists of, C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 aromatic hydrocarbon, like toluene.
  • Suitable transition metal compounds are in particular transition metal compounds (CT) of transition metals of groups 4 to 6, in particular of group 4 or 5, of the periodic table (IUPAC).
  • CT transition metal compounds
  • Suitable examples include Ti and V, in particular preferred is a compound of Ti, like TiCl 4 .
  • the catalyst component can comprise e.g. reducing agents, like compounds of group 13, preferably Al-compounds containing alkyl and/or alkoxy residues, and optionally halogen residues. These compounds can be added into the catalyst preparation at any step before the final recovery.
  • the olefin polymerization catalyst used in the invention may comprise in addition to the catalyst components (solid catalyst system) conventional cocatalyst, e.g. those based on compounds of group 13 of the periodic table (IUPAC), e.g. organo aluminum, such as aluminum compounds, like aluminum alkyl, aluminum halide or aluminum alkyl halide compounds (e.g. triethylaluminum) compounds, can be mentioned.
  • solid catalyst system conventional cocatalyst, e.g. those based on compounds of group 13 of the periodic table (IUPAC), e.g. organo aluminum, such as aluminum compounds, like aluminum alkyl, aluminum halide or aluminum alkyl halide compounds (e.g. triethylaluminum) compounds, can be mentioned.
  • IUPAC periodic table
  • one or more external donors can be used which may be typically selected e.g. from silanes or any other well known external donors in the field. External donors are known in the art and are used as stereoregulating agent in propylene polymerization. The external donors are preferably selected from hydrocarbyloxy silane compounds and hydrocarbyloxy alkane compounds.
  • Typical hydrocarbyloxy silane compounds have the formula (II) R' 0 Si(OR") 4-0 (II) wherein
  • the alkoxy silane compound having the formula (II) is dicyclopentyl dimethoxy silane or cyclohexylmethyl dime
  • the solid catalyst system (SCS) according to the emulsion method is obtained by
  • the complex (C) is preferably dissolved in an C 6 to C 10 aromatic hydrocarbon, like toluene and contacted with a liquid transition metal compound (CT), preferably with a liquid transition metal compound (CT) of transition metals of groups 4 to 6, in particular of group 4, of the periodic table (IUPAC), like Ti (e.g. TiCl 4 ).
  • CT liquid transition metal compound
  • IUPAC periodic table
  • Ti e.g. TiCl 4
  • the production of a two-phase, i.e. of an emulsion is encouraged by carrying out the contacting at low temperature, specifically above 10 °C but below 60 °C, preferably between above 20 °C and below 50 °C.
  • the emulsion comprises a continuous phase and a dispersed phase in form of droplets. In the dispersed phase the complex (C) as well as the transition metal compound (CT) are present
  • Additional catalyst components like an aluminium compound, like aluminium alkyl, aluminium alkyl halide or aluminium alkoxy or aluminium alkoxy alkyl or halide or other compounds acting as reducing agents can be added to the reactions mixture at any step before the final recovery of the solid catalyst system (SCS).
  • any agents enhancing the emulsion formation can be added.
  • emulsifying agents or emulsion stabilisers e.g. surfactants, like acrylic or metacrylic polymer solutions and turbulence minimizing agents, like alpha-olefin polymers without polar groups, like polymers of alpha olefins of 6 to 20 carbon atoms.
  • Suitable processes for mixing the obtained emulsion include the use of mechanical as well as the use of ultrasound for mixing, as known to the skilled person.
  • the process parameters such as time of mixing, intensity of mixing, type of mixing, power employed for mixing, such as mixer velocity or wavelength of ultrasound employed, viscosity of solvent phase, additives employed, such as surfactants, etc. are used for adjusting the size of the solid catalyst system particles (SCS).
  • SCS solid catalyst system particles
  • Said solid catalyst system particles may then be formed and recovered in usual manner, including the solidification of the catalyst particles by heating (for instance at a temperature of 70 to 150 °C, more preferably at 90 to 110 °C) and separating steps (for recovering the catalyst particles).
  • heating for instance at a temperature of 70 to 150 °C, more preferably at 90 to 110 °C
  • separating steps for recovering the catalyst particles.
  • the catalyst particles obtained may furthermore be subjected to further post-processing steps, such as washing, stabilizing, prepolymerization, prior to the final use in polymerisation process.
  • the solid catalyst system (SCS) contains inclusions, like catalytically inactive solid material, reference is made to WO 2007/077027 , and EP 2 065 405 .
  • the solid catalyst system (SCS) according to the precipitation method is obtained by:
  • the complex (C) is preferably dissolved in an C 6 to C 10 aromatic hydrocarbon, like toluene and contacted with a liquid transition metal compound (CT), i.e with a transition metal compound (CT) being not solid.
  • CT transition metal compound
  • the transition metal compound (CT) as such is a liquid or it is dissolved in a solvent at ambient temperatures, i.e. at temperatures up to 80 °C (20 to 80 °C).
  • a solvent is used for the transition metal compound (CT), it can be any organic solvent and can be the same as the organic solvent used for the complex (C) or can be different thereto, the latter being preferred.
  • the organic solvent for the transition metal compound (CT) is C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 alkane, like heptanes, octane or nonane, or any mixtures thereof.
  • the transition metal compound (CT) is preferably a transition metal compound (CT) of transition metals of groups 4 to 6, in particular of group 4, of the periodic table (IUPAC), like Ti (e.g. TiCl 4 ). Due to the contact of the solution of the complex (C) with the liquid transition metal compound (CT) or with a solution of the transition metal compound (CT) precipitation occurs and the solid catalyst system (SCS) is formed.
  • precipitation means that during the catalyst preparation a chemical reaction in a solution takes place leading to the desired catalyst system (SCS) insoluble in said solution.
  • SCS catalyst system
  • Such a precipitated solid catalyst system (SCS) is different in form and shape to a solid catalyst system (SCS) obtained by the emulsion method discussed above.
  • the combining of the solution of the complex (C) with the liquid transition metal compound (CT) or with the solution of the transition metal compound (CT) is effected at a temperature of at least 50 °C, preferably in the temperature range of 50 to 110 °C, like in the temperature range of 70 to 100 °C, most preferably in the range of 85 to 95 °C. It is especially appreciated that after having combined the complex (C) and the transition metal compound (CT) that the whole reaction mixture is kept at least at 50 °C, more preferably is kept in the temperature range of 50 to 110 °C, like 70 to 100 °C, most preferably in the range of 85 to 95 °C, to secure full precipitation of the catalyst in form of a solid particle.
  • a precipitating agent according to this invention is an agent which promotes the precipitation of the catalyst system (SCS) in form of a solid particle.
  • SCS catalyst system
  • the organic solvent used for the transition metal compound (CT) can promote the precipitating and thus act and used as a precipitating agent.
  • the final catalyst does not contain such a medium.
  • the catalyst system (SCS) used in the present application is free of any precipitating agent residues. "Free” in this context throughout the invention means that not more than 1.0 wt.-%, preferably not more than 0.5 wt.-%, more preferably not more than 0.05 wt.-%, still more preferably not more than 0.005 wt.-%, yet more preferably no detectable precipitating agent is present within the solid catalyst system (SCS).
  • Additional catalyst components like the cocatalyst and/or the external donor, as described above, can be used as normally in olefin polymerisation catalyst.
  • Suitable mixing techniques include the use of mechanical as well as the use of ultrasound for mixing, as known to the skilled person.
  • the solvent for the complex (C) on the one hand and the solvent of the transition metal compound (CT) on the other hand are selected in a way which supports the immediate precipitation of the solid catalyst system (SCS).
  • the solvent for the complex (C) comprises, preferably consists of, C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 aromatic hydrocarbon, like toluene.
  • the solvent where the transition metal compound (CT), like TiCl 4 , can be solved, can be the same as for the complex (C) or can be different thereto, the latter being preferred.
  • the solvent for the transition metal compound (CT) is C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 alkane, like heptanes, octane or nonane, or any mixtures thereof. It is in particular appreciated that the solvent for the complex (C) is C 6 to C 10 aromatic hydrocarbon, like toluene, and the solvent for the transition metal compound (CT) is a C 6 to C 10 alkane, like heptanes.
  • solid catalyst particle After precipitation the solid catalyst particle is washed in a known manner. Accordingly it is preferred that solid catalyst particle is washed with toluene, preferably with hot (e. g. 90 °C) toluene and subsequently with heptane, most preferably with hot (e. g. 90 C) heptane. Further washings, e.g. with gold heptanes, or pentane are possible as well.
  • SCS solid catalyst system
  • the polymerization process for producing the polypropylene as defined in the instant invention can be any known process, with the proviso that the catalyst comprising the catalyst system (SCS) as defined herein is employed.
  • propylene and optionally ethylene and/or at least one C 4 to C 10 ⁇ -olefin is/are polymerized in the presence of the catalyst comprising the solid catalyst system (SCS) to obtain the polypropylene (PP) as defined in the instant invention.
  • the process for the manufacture of the instant polypropylene (PP) can be a single stage process using a liquid phase, slurry phase or gas phase reactor.
  • the polypropylene (PP) is produced in a multistage process, comprising at least one slurry (bulk) phase reaction and at least one additional slurry and/or gas phase reactor in which the catalyst comprising the solid catalyst system (SCS) of the instant invention is employed.
  • a preferred multistage process is a slurry-gas phase process, such as developed by Borealis and known as the Borstar® technology.
  • a slurry-gas phase process such as developed by Borealis and known as the Borstar® technology.
  • EP 0 887 379 A1 WO 92/12182
  • WO 2004/000899 WO 2004/111095
  • WO 99/24478 WO 99/24479
  • WO 00/68315 are incorporated herein by reference.
  • a further suitable slurry-gas phase process is the Spheripol ® process of Basell.
  • the polypropylene (PP) is produced in the Spheripol ® or in the Borstar ® -PP process.
  • the polypropylene (PP) which is used for the preparation of the capacitor film is preferably prepared by polymerizing, in a slurry reactor, for example a loop reactor, propylene optionally together with at least another C 2 to C 10 ⁇ -olefin (comonomers), in the presence of the catalyst comprising the solid catalyst system (SCS) to produce a part of the polypropylene (PP).
  • a slurry reactor for example a loop reactor
  • SCS solid catalyst system
  • This reaction sequence provides a reactor blend of parts (i) (fraction (A)) and (ii) (fraction (B)) constituting a polypropylene (PP).
  • the first reaction is carried out in a gas phase reactor while the second polymerization reaction is carried out in a slurry reactor, for example a loop reactor.
  • a slurry reactor for example a loop reactor.
  • additional polymerization reactors, and prepolymerization reactors In addition to the reactors above it is possible to use additional polymerization reactors, and prepolymerization reactors.
  • the above-discussed process comprising at least two polymerization steps, is advantageous in view of the fact that it provides easily controllable reaction steps enabling the preparation of a desired reactor blend.
  • the polymerization steps may be adjusted, for example by appropriately selecting monomer feed, comonomer feed, hydrogen feed, temperature and pressure in order to suitably adjust the properties of the polymerization products obtained.
  • the reaction product of the slurry polymerization which preferably is carried out in a loop reactor, is then transferred to the subsequent gas phase reactor, wherein the temperature preferably is within the range of from 50 to 130 °C, more preferably 70 to 100 °C, at a pressure in the range of from 5 to 50 bar, preferably 15 to 35 bar, again with the option of adding hydrogen in order to control the molecular weight.
  • the properties of the polypropylene (PP) produced with the above-outlined process may be adjusted and controlled with the process conditions as known to the skilled person, for example by one or more of the following process parameters: temperature, hydrogen feed, comonomer feed, propylene feed, catalyst type and amount of external donor, split between two or more components of a multimodal polymer.
  • the polypropylene (PP) is subjected to a film forming process. Any film forming processes which are suitable for the manufacture of a capacitor film can be used.
  • the capacitor film i.e. the biaxially oriented polypropylene (BOPP)
  • BOPP biaxially oriented polypropylene
  • the process for the manufacture of a capacitor film, i.e. the biaxially oriented polypropylene (BOPP) comprises the use of the polypropylene (PP) as defined herein and its forming into a film preferably by the tenter method known in the art.
  • the tenter method is in particular a method in which the polypropylene (PP) as defined herein is melt extruded from a slit die such as a T-die and cooled on a cooling drum obtaining an undrawn sheet.
  • Said sheet is pre-heated for example with a heated metal roll and then drawn in the length direction between a plurality of rolls over which a difference in peripheral speeds is established and then both edges are gripped with grippers and the sheet is drawn in the transverse direction in an oven by means of a tenter resulting in a biaxially drawn film.
  • the temperature of said stretched sheet during the longitudinal drawing is preferably controlled in such a way as to be within the temperature range of the melting point of the polypropylene as defined herein (machine direction: -20 to -5°C; transverse direction: -10 to +15°C).
  • the uniformity of the film thickness on transverse drawing can be evaluated with the method in which a fixed region on the film is masked after drawing in the length direction and measuring the actual drawing factor by measuring the spacing of the said masking after transverse drawing.
  • the capacitor film i.e. the biaxially oriented film (BOPP)
  • the capacitor film can be treated by corona discharge in air, nitrogen, carbon dioxide gas or any of the mixtures on the surface to be metalized, to improve the adhesive strength to the metal to be deposited, and wound by a winder.
  • BOPP biaxially oriented film
  • the present specification further describes the use of a polypropylene (PP) having
  • the polypropylene (PP) is further defined as indicated above. It is in particular appreciated that the polypropylene (PP) is biaxially oriented, preferably has biaxially stretched with ratios indicated above.
  • the present invention is directed to a capacitor comprising at least one layer comprising a capacitor film as defined herein. Additionally it is preferred that the capacitor comprises a metal layer, in particular a metal layer obtained by the above described process.
  • Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the isotacticity, regio-regularity and comonomer content of the polymers.
  • Quantitative 13 C ⁇ 1 H ⁇ NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for 1 H and 13 C respectively. All spectra were recorded using a 13 C optimised 10 mm extended temperature probehead at 125°C using nitrogen gas for all pneumatics.
  • the tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest( Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443 ; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A.L., Macromoleucles 30 (1997) 6251 ).
  • the mole fraction of ethylene in the polymer was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through integration of multiple signals across the whole spectral region of a 13 C ⁇ 1 H ⁇ spectra acquired using defined conditions. This method was chosen for its accuracy, robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability to a wider range of comonomer contents.
  • the comonomer sequence distribution at the triad level was determined using the method of Kakugo et al. ( Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150 ) through integration of multiple signals across the whole spectral region of a 13 C ⁇ 1 H ⁇ spectra acquired using defined conditions. This method was chosen for its robust nature. Integral regions were slightly adjusted to increase applicability to a wider range of comonomer contents.
  • Mw, Mn molecular weight distribution
  • Mw molecular weight distribution
  • PDI polydispersity index
  • the molar mass at each elution slice was determined by light scattering using a combination of two angels 15° and 90°. All data processing and calculation was performed using the Cirrus Multi-Offline SEC-Software Version 3.2 (Polymer Laboratories a Varian inc. Company). The molecular weight was calculated using the option in the Cirrus software "use combination of LS angles" in the field "sample calculation options subfield slice MW data from”.
  • Mw i K LS * R ⁇ ⁇ 90 ⁇ ° d n d c * R * P ⁇
  • the Rayleigh ratio R( ⁇ ) 90 ° of the 90° angle is measured by the LS detector and R is the response of the RI-detector.
  • the particle scatter function P( ⁇ ) is determined by the usage of both angles (15° and 90°) as described by C. Jackson and H. G. Barth( C. Jackson and H. G. Barth, "Molecular Weight Sensitive Detectors” in Handbook of Size Exclusion Chromatography and related techniques, C.-S. Wu, 2nd ed., Marcel Dekker, New York, 2004, p.103 ).
  • a linear fit was used to correlate the elution volume to the corresponding molecular weight.
  • the dn/dc used in the equation is calculated from the detector constant of the RI detector, the concentration c of the sample and the area of the detector response of the analysed sample.
  • the relative amount of branching is determined using the g'-index of the branched polymer sample.
  • [ ⁇ ] is the intrinsic viscosity at 160 °C in trichloorbenzene of the polymer sample at a certain molecular weight and is measured by an online viscosity and a concentration detector. The intrinsic viscosities were measured as described in the handbook of the Cirrus Multi-Offline SEC-Software Version 3.2 with use of the Solomon-Gatesman equation.
  • the necessary concentration of each elution slice is determined by a RI detector.
  • [ ⁇ ] lin is the intrinsic viscosity of a linear sample and [ ⁇ ] br the viscosity of a branched sample of the same molecular weight and chemical composition.
  • MFR 2 (230 °C) is measured according to ISO 1133 (230 °C, 2.16 kg load)
  • Tensile modulus in machine direction was determined according to ISO 527-3 at 23°C on the biaxially oriented films. Testing was performed at a cross head speed of 1 mm/min. Electrical breakdown strength (EB63%) The electrical breakdown strength was measured according to IEC 60243-2(1998). The obtained raw data was evaluated according to IEC 60727, part 1 & 2
  • the method (IEC 60243-2) describes a way to measure the electrical breakdown strength for insulation materials on compression moulded plaques.
  • the electrical breakdown strength is determined within a high voltage cabinet using metal rods as electrodes as described in IEC 60243-2 .
  • the voltage is raised over the film/plaque at 2 kV/s until a breakdown occurs.
  • Electrical conductivity was calculated as the inverse of the electrical resistance as determined in accordance to ASTM D257.
  • Porosity BET with N 2 gas, ASTM 4641, apparatus Micromeritics Tristar 3000; sample preparation: at a temperature of 50 °C, 6 hours in vacuum.
  • Ash content is measured according to ISO 3451-1 (1997)
  • Mean particle size (d50) is given in nm and measured with Coulter Counter LS200 at room temperature with n-heptane as medium, particle sizes below 100 nm by transmission electron microscopy.
  • Particle size (d10) is given in nm and measured with Coulter Counter LS200 at room temperature with n-heptane as medium.
  • Particle size (d90) is is given in nm and measured with Coulter Counter LS200 at room temperature with n-heptane as medium.
  • SPAN is defined as follows: d ⁇ 90 ⁇ m - d ⁇ 10 ⁇ m d ⁇ 50 ⁇ m
  • Solid Catalyst system used in the present invention was prepared according to example 8 of WO2004/029112 , except that diethylaluminium chloride was used as an aluminium comound instead of triethyl aluminium.
  • Polymer was produced in prepolymerisation reactor of 50 m 3 , one slurry loop reactor of 150 m 3 and one gas phase reactor with the process parameters (Table 1)
  • the solid catalyst system was as described in Catalyst preparation - IE1.
  • co-catalyst triethyl-aluminium (TEA) was used, and dicyclopentyldimethoxysilane was used as external donor.
  • CE1 is commercially available very high purity "Borclean HB311BF" propylene homopolymer grade of Borealis AG for dielectric applications, which has MFR 2 (230°C) of 2.2 g/10 min, T m (DSC, ISO 3146) of 161 to 165°C, very low ash content 10-20 ppm (measured by ISO 3451-1) and has been produced by a TiCl 3 based Ziegler-Natta catalyst. The commercial product has been further purified after the polymerization to reduce the catalyst residues.
  • Table 3 Film properties CE 1 IE 1 Thickness [ ⁇ m] 7.0 7.0 Electrical property Amount of weak points [200 V/ ⁇ m - #/m 2 ] 0.04 0 [250 V/ ⁇ m - #/m 2 ] 0.07 0.09 [300 V/ ⁇ m - #/m 2 ] 0.27 0.13 [350 V/ ⁇ m - #/m 2 ] 0.6 0.32 [400 V/ ⁇ m - #/m 2 ] n.a. 0.6 FS [VDC/ ⁇ m] 740 675
  • Field strength at break down 100 °C, resistance, Tan ⁇ at 80 °C and resistance and electrical conductivity have values generally accepted for polypropylene in capacitor films.

Claims (15)

  1. Verfahren zur Herstellung eines Kondensatorfilms, umfassend die Schritte
    (a) Polymerisieren von Propylen und gegebenenfalls Ethylen und/oder mindestens einem C4 bis C10 α-Olefin in der Gegenwart eines Katalysators, umfassend ein ungeträgertes Katalysatorsystem als Feststoff (SCS), um ein Polypropylen (PP) zu erhalten,
    (b) Unterziehen des Polypropylens (PP) einem Filmbildungsprozess, um
    einen Kondensatorfilm zu erhalten,
    wobei in dem Polymerisationsschritt (a) der Katalysator, umfassend das Katalysatorsystem als Feststoff (SCS) zu Katalysatorfragmenten (F) im Nanometerbereich fragmentiert, welche in dem Polypropylen (PP) verteilt sind, wobei das Katalysatorsystem als Feststoff (SCS) umfasst
    (i) eine Verbindung eines Übergangsmetalls, wobei das Metall vorzugsweise ausgewählt ist aus einer der Gruppen 4 bis 6, insbesondere Gruppe 4, wie etwa Ti, des Periodensystems (IUPAC),
    (ii) eine Verbindung eines Metalls, wobei das Metall ausgewählt ist aus einer der Gruppen 1 bis 3 des Periodensystems (IUPAC), und
    (iii) einen Elektronendonor (E).
  2. Verfahren gemäß Anspruch 1, wobei das Katalysatorsystem als Feststoff (SCS) erhalten wird durch ein Verfahren umfassend Kontaktieren
    (c) einer Lösung eines Komplexes (C) eines Metalls, welches ausgewählt ist aus einer der Gruppen 1 bis 3 des Periodensystems (IUPAC), und eines Elektronendonors (E), wobei der Komplex (C) erhalten wird durch Umsetzen einer Verbindung (CM) des Metalls mit dem Elektronendonor (E) oder einem Vorläufer (EP) davon,
    mit
    (d) einer flüssigen Übergangsmetallverbindung (CT) oder einer Lösung einer Übergangsmetallverbindung (CT).
  3. Verfahren zur Herstellung eines Kondensatorfilms, umfassend die Schritte
    (a) Polymerisieren von Propylen und gegebenenfalls Ethylen und/oder mindestens einem C4 bis C10 α-Olefin in der Gegenwart eines Katalysators, umfassend ein Katalysatorsystem als Feststoff (SCS), um Polypropylen (PP) herzustellen,
    (b) Unterziehen des Polypropylens (PP) einem Filmbildungsprozess, um
    dadurch einen Kondensatorfilm zu erhalten,
    wobei das Katalysatorsystem als Feststoff (SCS) aus Schritt (a) erhalten wird durch ein Verfahren, umfassend Kontaktieren
    (c) einer Lösung eines Komplexes (C) eines Metalls, welches ausgewählt ist aus einer der Gruppen 1 bis 3 des Periodensystems (IUPAC), und einem Elektronendonor (E), wobei der Komplex (C) erhalten wird durch Umsetzen einer Verbindung (CM) des Metalls mit dem Elektronendonor (E) oder einem Vorläufer (EP) davon, mit
    (d) einer flüssigen Übergangsmetallverbindung (CT) oder einer Lösung einer Übergangsmetallverbindung (CT).
  4. Verfahren gemäß Anspruch 3, wobei der Katalysator, umfassend das Katalysatorsystem als Feststoff (SCS) in dem Polymerisationsschritt (a) zu Katalysatorfragmenten (F) im Nanometerbereich fragmentiert, wobei die Katalysatorfragmente (F) im Nanometerbereich in dem Polypropylen (PP) verteilt sind.
  5. Verfahren gemäß Anspruch 3 oder 4, wobei das Katalysatorsystem als Feststoff (SCS) umfasst
    (i) eine Verbindung eines Übergangsmetalls, welches vorzugsweise ausgewählt ist aus einer der Gruppen 4 bis 6, insbesondere Gruppe 4, wie etwa Ti, des Periodensystems (IUPAC),
    (ii) eine Verbindung eines Metalls, wobei das Metall ausgewählt ist aus einer der Gruppen 1 bis 3 des Periodensystems (IUPAC), und
    (iii) einen (internen) Elektronendonor (E).
  6. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Polypropylen (PP) aufweist
    (a) <2,1> Erythroregiodefekte von gleich oder weniger als 0,4 Mol.-%,
    bestimmt durch 13C-NMR-Spektroskopie,
    und/oder
    (b) eine Durchschlagsspannung bei 100°C von mindestens 350 VDC/µm, gemessen mit einem biaxial gereckten Polypropylenfilm (BOPP), hergestellt aus dem Polypropylen (PP) mit einem Reckverhältnis in Längsrichtung und in Querrichtung von 4,5 x 9,5.
  7. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Katalysatorsystem als Feststoff (SCS)
    (a) eine spezifische Oberfläche, gemessen gemäß ASTM D 3663 von
    weniger als 20 m2/g aufweist
    und/oder
    (b) katalytisch inaktives festes Material umfasst, wobei das Material gegebenenfalls aufweist
    (b1) eine spezifische Oberfläche von weniger als 500 m2/g, und/oder
    (b2) eine mittlere Teilchengröße (d50) von weniger als 200 nm.
  8. Verfahren gemäß einem der vorstehenden Ansprüche, wobei das Polypropylen (PP) ist
    (a)
    (i) ein Propylenhomopolymer,
    oder
    (ii) ein Propylen-Random-Copolymer mit einem Comonomergehalt von gleich oder weniger als 1,0 Gew.-%, wobei die Comonomere Ethylen und/oder mindestens ein C4 bis C10 α-Olefin sind,
    und/oder
    (b) keinem Waschschritt unterzogen wird.
  9. Verfahren gemäß einem der vorstehenden Ansprüche, wobei der Filmbildungsprozess ein Reckverfahren ist, in welchem das Polypropylen (PP) in Längsrichtung und in Querrichtung gereckt wird, wobei vorzugsweise das Reckverhältnis in beide Richtungen mindestens 4,0 beträgt.
  10. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 5 und 7, wobei das Katalysatorsystem als Feststoff (SCS) erhalten wird durch
    (a) Herstellen einer Lösung eines Komplexes (C) eines Metalls, welches ausgewählt ist aus einer der Gruppen 1 bis 3 der Periodensystems (IUPAC), und eines Elektronendonors (E), wobei der Komplex (C) erhalten wird durch Umsetzen einer Verbindung (CM) des Metalls mit dem Elektronendonor (E) oder einem Vorläufer (EP) davon in einem organischen Lösungsmittel,
    (b) Vermischen der Lösung von Komplex (C) mit einer flüssigen Übergangsmetallverbindung (CT),
    (c) dadurch Erhalten einer Emulsion einer kontinuierlichen Phase und einer dispergierten Phase, wobei die dispergierte Phase in Form von Tröpfchen vorliegt und den Komplex (C) und die Übergangsmetallverbindung (CT) umfasst,
    (d) Verfestigen der Tröpfchen der dispergierten Phase, wobei dadurch das Katalysatorsystem als Feststoff (SCS) erhalten wird.
  11. Verfahren gemäß Anspruch 10, wobei
    (a) ein Surfactant verwendet wird, um die Emulsion zu bilden und/oder
    zu stabilisieren,
    und/oder
    (b) die Temperatur bei der Bildung der Emulsion gleich oder weniger als 60°C ist.
  12. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 5 und 7, wobei das Katalysatorsystem als Feststoff (SCS) erhalten wird durch
    (a) Herstellen einer Lösung eines Komplexes (C) eines Metalls, welches ausgewählt ist aus einer der Gruppen 1 bis 3 des Periodensystems (IUPAC), und eines Elektronendonors (E), wobei der Komplex (C) erhalten wird durch Umsetzen einer Verbindung (CM) des Metalls mit dem Elektronendonor (E) oder einem Vorläufer (EP) davon in einem organischen Lösungsmittel,
    (b) Kombinieren der Lösung von Komplex (C) mit einer flüssigen Übergangsmetallverbindung (CT) oder einer Lösung einer Übergangsmetallverbindung (CT), was zum Ausfällen des Katalysatorsystems (SCS) in der Form von festen Partikeln führt.
  13. Verfahren gemäß Anspruch 12, wobei
    (a) die Temperatur beim Ausfällen mindestens 50°C beträgt, und/oder
    (b) keine Emulsion bei der Herstellung des Katalysatorsystems als
    Feststoff (SCS) gebildet wird,
    und/oder
    (c) entweder die Lösung von Komplex (C) oder die flüssige Übergangsmetallverbindung (CT) bzw. die Lösung einer Übergangsmetallverbindung (CT) festes Material enthält.
  14. Verfahren gemäß einem der vorstehenden Ansprüche 1 bis 5, 7 und 10 bis 13, wobei
    (a) das Lösungsmittel zur Herstellung einer Lösung des Komplexes (C) einen aromatischen Kohlenwasserstoff umfasst, vorzugsweise ein aromatischer Kohlenwasserstoff ist,
    und/oder
    (b) das Lösungsmittel zur Herstellung einer Lösung der Übergangsmetallverbindung (CT) einen C5 bis C10 Kohlenwasserstoff umfasst, vorzugsweise ein C5 bis C10 Kohlenwasserstoff ist.
  15. Verfahren gemäß einem der vorstehenden Ansprüche, wobei nach der Filmbildung der erhaltene Kondensatorfilm metallisiert wird.
EP11179322.0A 2011-08-30 2011-08-30 Verfahren zur herstellung eines kondensatorfilms Active EP2565221B2 (de)

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CN201280041262.1A CN103764732B (zh) 2011-08-30 2012-08-29 用于制造电容器膜的方法
PCT/EP2012/066729 WO2013030210A1 (en) 2011-08-30 2012-08-29 Process for the manufacture of a capacitor film
US14/240,696 US10253115B2 (en) 2011-08-30 2012-08-29 Process for the manufacture of a capacitor film
KR1020147007757A KR101663393B1 (ko) 2011-08-30 2012-08-29 커패시터 필름의 제조 방법
SG2014011357A SG2014011357A (en) 2011-08-30 2012-08-29 Process for the manufacture of a capacitor film
JP2014527636A JP5789721B2 (ja) 2011-08-30 2012-08-29 キャパシタフィルムの製造方法

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EP2565221A1 (de) 2013-03-06
JP2014531480A (ja) 2014-11-27
KR20140054348A (ko) 2014-05-08
KR101663393B1 (ko) 2016-10-06
EP2565221B2 (de) 2018-08-08
CN103764732A (zh) 2014-04-30
JP5789721B2 (ja) 2015-10-07
CN103764732B (zh) 2016-06-08
US20140220236A1 (en) 2014-08-07
WO2013030210A1 (en) 2013-03-07
SG2014011357A (en) 2014-08-28
US10253115B2 (en) 2019-04-09

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